109539-16-4Relevant academic research and scientific papers
Copper-catalyzed reactions of organotitanium reagents. Highly selective SN2′-allylation and conjugate addition
Arai, Masayuki,Lipshutz, Bruce H.,Nakamura, Eiichi
, p. 5709 - 5718 (2007/10/02)
In the presence of a catalytic amount of CuI·ILiCl, alkyltitanium (RTi(O-I-Pr)3) and titanate reagents (RnTi(O-i-Pr)5-nLi) undergo highly selective SN2′-alkylation reactions with allylic chlorides and allylic diethylphosphates in high yields. The regioselectivity of the reaction is as high as 99.8%. The reaction proceeds with excellent anti-stereoselectivity with respect to the nucleophile and the leaving group, and exhibits high 1,2-anti-diastereoselectivity with a δ-chiral allylic chloride. The catalytic copper reagent is also a mild agent to transfer an alkyl group to an enone in the presence of Me3SiCl. The alkyltitanium-based catalytic reagent selectively reacts with an allylic phosphate rather than with an enone, while in the presence of a silicon activator, it reacts preferentially with the enone rather than with the phosphate. 1H NMR studies on a mixture of Me2CuLi and TiCl(O-i-Pr)3 provided information on reagent composition.
Copper-Catalyzed Reactions of Organotitanium Reagents. Highly SN2'- and Anti-Selective and Diastereo- and Chemoselective Alkylation of Allylic Chlorides and Phosphates
Arai, Masayuki,Nakamura, Eiichi,Lipshutz, Bruce H.
, p. 5489 - 5491 (2007/10/02)
Organotitanium reagents undergo Cu(I)-catalyzed SN2' substitution reactions with allylic chlorides and phosphates in a regio-, stereo-, and chemoselective manner: in the presence of Me3SiCl or Me3SiOSO2CF3, they undergo preferential conjugate addition to enones.
ORGANOMANGANESE (II) REAGENTS XVI: COPPER-CATALYZED 1,4-ADDITION OF ORGANOMANGANESE CHLORIDES TO CONJUGATED ENONES
Cahiez, Gerard,Alami, Mouad
, p. 3541 - 3544 (2007/10/02)
Copper-catalyzed conjugate addition of organomanganese chlorides to conjugated enones in THF, at 0 deg C, leads to the 1,4-addition products in high yields.The scope of the reaction is very large and the results are generally better than those obtained from organomagnesium compounds in the presence of a copper salts as well as from organocopper or cuprate reagents.Furthermore organomanganese chlorides are indisputably cheaper and more stable than the latter.
